[Pd{CpFe[η5-C5H2{C(H)O(CH2)3O}C(H)][N=2,4,6-Me3C6H2]}(μ-Cl)]2 | 1356834-37-1

• 英文名称: [Pd{CpFe[η5-C5H2{C(H)O(CH2)3O}C(H)][N=2,4,6-Me3C6H2]}(μ-Cl)]2
• 英文别名: [Pd{CpFe[η⁵-C5H2{C(H)O(CH2)3O}C(H)][N=2,4,6-Me3C6H2]}(μ-Cl)]2；[PdCl(η5-C5H5)Fe(η5-C5H2(C(H)O(CH2)3O)C(H)=N-2,4,6-Me3C6H2)]2
• CAS: 1356834-37-1
• 化学式: C₄₈H₅₂Cl₂Fe₂N₂O₄Pd₂
• 分子量: 1116.39
• InChiKey: YCQBNYORWOUDNK-OHCGRGDMSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  [Pd{CpFe[η5-C5H2{C(H)O(CH2)3O}C(H)][N=2,4,6-Me3C6H2]}(μ-Cl)]2 、 三苯基膦 以 丙酮 为溶剂， 反应 24.0h， 以54.35%的产率得到[Pd{CpFe[η⁵-C5H2{C(H)O(CH2)3O}C(H)N=2,4,6-Me3C6H2]}(Cl)(PPh3)]
  参考文献：
  名称：

  Versatile reactivity of dioxaneferrocenylimine palladacycles by controlled acid hydrolysis. Crystal and molecular structure of [Pd{CpFe[η5-C5H2{CH(OMe)2}C(H)N-2,4,6-Me3C6H2]}(Cl)(PPh2Et)]

  摘要：

  Treatment of a or b with Li-2[PdCl4] in methanol at room temperature for 48 h, gave the tetrametallic chlorine bridged complexes [Pd{CpFe[eta(5)-C5H2{C(H)O(CH2)(3)O}C(H)=NR]}(mu-Cl)](2), 1a and 1b, containing a cyclic acetal on the metallated cyclopentadienyl ring. The reactions of 1a and 1b with the Ph2P(CH2)(n)PPh2 diphosphines in a 1:1 ratio gave the tetrametallic species [{Pd{CpFe[eta(5)-C5H2{C(H) O(CH2)(3)O}C(H)=NR]}(Cl)}(2)(mu-Ph2P(CH2) nPPh(2))], n = 1-4 as appropriate, 2a-5a and 2b-5b, with the diphosphine in a bridging mode and terminal chlorine ligands. Treatment of 1a and 1b with monophosphines yielded the dimetallic compounds [Pd{CpFe[eta(5)-C5H2{C(H)O(CH2)(3)O}C(H)=NR]}(Cl)(L)] (L = PPh3, PPh2Me, PPh2Et) 6a-8a and 6b-7b. Reaction of the phosphine derivatives with aqueous acetic acid gave the corresponding functionalized compounds with transformation of the 1,3-dioxane ring into a formyl group on the metallated ring 9a-15a and 9b-14b. Reaction of 8a with acetic acid in methanol gave [Pd{CpFe[eta(5)-C5H2{CH(OMe)(2)}C(H)=N-2,4,6-Me3C6H2]}(Cl)(PPh2Et)] 16a, after a transacetalization reaction with an acetal moiety -CH(OMe)(2) on the metallated five-membered ring. The molecular structure of compound 16a has been determined by X-ray diffraction analysis. (C) 2013 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2013.05.007
• 作为产物：
  描述：

  [(η5-C5H5)Fe(η5-C5H3(C(H)O(CH2)3O)C(H)=N-2,4,6-Me3C6H2)] 、 palladium dichloride 在 LiCl 、 NaOAc 作用下， 以 甲醇 为溶剂， 以72%的产率得到[Pd{CpFe[η5-C5H2{C(H)O(CH2)3O}C(H)][N=2,4,6-Me3C6H2]}(μ-Cl)]2
  参考文献：
  名称：

  Dioxaneferrocenylimine Cyclometalated Compounds as Precursors to Novel Functionalized Di- and Tetranuclear Metallacycles Leading to 1,3-Double Palladation of an η⁵-C₅H₅ Ring

  摘要：

  Reaction of the Schiff base ligands CpFe[eta(5)-C6H2{C(H)O(CH2)(3)O}C(H)=NR] (R = 2,4,6-Me3C6H2, a; R = Cy, b) derived from the 1,2-disubstituted formylferrocene CpFe[(CHO){C(H)O(CH2)(3)O}-eta(5)-C5H3] 1, with Li-2[PdCl4] in methanol at room temperature for 48 h, gave the chlorine-bridged complexes [Pd{CpFe[eta(5)-C5H2{C(H)O(CH2)(3)O}C-(H)=NR])(Cl)}(2), 1a and 1b, after C-H activation of the cyclopentadienyl ring bearing the cyclic acetal. The reactions of 1a and 1b with the Ph2P(CH2)PPh2 diphosphines in a 1:2 ratio, plus addition of ammonium hexafluorophosphate, gave the dinucelar compounds [Pd{CpFe[eta(5)-C5H2{C(H)O(CH2)(3)O}C(H)=NR}}-(Ph2P(CH2)(n) PPh2-P,P)][PF6] 2a, 3a and 2b, 3b with the diphosphine in a chelating mode, as 1:1 electrolytes. Treatment of the latter with aqueous acetic acid gave the corresponding functionalized compounds with transformation of the 1,3-dioxane ring into a formyl group on the metalated ring, 4a, 5a and 4b, 5b. The Schiff base condensation reaction of 5b with 2-(methylthio)aniline in refluxing chloroform gave [Pd(Ph2P(CH2)(2)PPh2)-{(CPFe)eta(5)-C5H2[C(H)=NCy][C(H)=N(2-SMeC6H4]}][PF6] 6b, with regeneration of the C=N double bond, which, when treated with lithium tetrachloropalladate in methanol for 48 h, gave the novel compound [Pd(Ph2P(CH2)(2)PPh2){(CpFe)eta(5)-C5H[C(H)=NCy][C(H)=N(2-SMeC6H4]}PdCl][PF6] 7b, which is the first ferrocene metallacyde displaying 1,3-double cyclopalladation.

  DOI：

  10.1021/om2008698